CN101219349A - Exchange membrane containing modified maleimide low polymer - Google Patents
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- CN101219349A CN101219349A CNA2007101624962A CN200710162496A CN101219349A CN 101219349 A CN101219349 A CN 101219349A CN A2007101624962 A CNA2007101624962 A CN A2007101624962A CN 200710162496 A CN200710162496 A CN 200710162496A CN 101219349 A CN101219349 A CN 101219349A
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Abstract
The invention relates to an exchange membrane with modified maleimide oligomer, which comprises sulfonyl polyaryl ether ketone and the modified maleimide oligomer. The exchange membrane is modified by malonylurea and takes the modified maleimide oligomer with hyper branched architecture as structure matrix, and the exchange membrane is led into the sulfonyl polyaryl ether ketone to form semi-IPN, thus strengthening water retaining capacity, anti-chemical properties, electrochemical stability and heat resistance of ion/proton exchange membranes. The exchange membrane can be used for producing membrane electrode assembly and fuel cell, or can be used in the field of seawater desalination, heavy water and sewage processing, biomass energy, and so on.
Description
Technical field
The present invention relates to a kind of exchange membrane that contains modified maleimide low polymer, refer in particular to a kind of ion/PEM that contains modified maleimide low polymer.
Background technology
In recent years, in the improvement of PEM film wood property energy, the lifting of battery pile (fuel cell stack) power density, and under the driving of factors such as catalyst price and use amount reduction, make Proton Exchange Membrane Fuel Cells have the ability of commercial competition gradually, the development potentiality of following application market is quite rich.
PEM has very important effect as solid electrolyte in Proton Exchange Membrane Fuel Cells, poly-perfluorinated ion-exchange membrane (perfluorinate ionomer membranes) is to set up best low temperature utilization section bar material at present, and it is the most general wherein to have excellent conductance with Nafion.Nafion is to be main chain with similar Teflon structure, hydrophilic cation exchange group sulfonic group (SO
3H) then be to connect with side chain to be suspended on the main chain.Basically, ion/PEM that the perfluorinated sulfonic acid fluidized polymer is made, its ionic conductivity is not poor and chemical stability is also good, but it is quite complicated on preparation engineering, and price is also very expensive, and because the mechanical strength deficiency of film makes the thickness of utilization often must surpass 100 μ m, cause ohmage to subtract and fall, influence the electrical conductivity of its ion/proton.
Non-fluorine ion/PEM serves as the research and development main shafts with sulfonated thermostable type thermoplastic polymer then, for example (poly (arylether ketones) PAEKs) has extensively been inquired into ion/proton exchange membrane material that research and exploitation have using value to the PAEK base polymer.Yet, ion/PEM that this polyaryl ether ketone polymer is made, must the moist environment more than certain degree in, could keep normal operational function.Therefore, only can use in the operating environment of 100 ℃ of following temperature, the territory of application can be limited to.And this exchange membrane has very high methanol permeability, can cause scurrying of methyl alcohol, and the polarization of negative electrode is significantly increased, and reduces the performance of battery.The above-mentioned result that these shortcomings produced tends to directly have influence on the conduction of proton and the transmission transmission mechanism of hydrone, and then reduces the overall efficiency of film.
Therefore, how promoting water holding capacity, the anti-chemistry and electrochemical stability, mechanical strength, hear resistance and flexibility of ion/PEM effectively, and subtract and fall cost of manufacture etc., should be the current problem that must pay attention to and solve.
Summary of the invention
Based on the problems referred to above, main purpose of the present invention is to provide a kind of exchange membrane that contains modified maleimide low polymer with high water holding capacity.
Another object of the present invention provides the good exchange membrane that contains modified maleimide low polymer of a kind of chemoresistance.
Another purpose of the present invention provides a kind of exchange membrane that contains modified maleimide low polymer with excellent electrochemical stability.
A further object of the present invention provides a kind of exchange membrane that contains modified maleimide low polymer of high-fire resistance.
For reaching above-mentioned and other purpose, the invention provides a kind of exchange membrane that contains modified maleimide low polymer, comprise sulfonated polyaryl ether ketone polymer and modified maleimide low polymer.Described exchange membrane is that Israel and Palestine have the modified maleimide low polymer of high branched structure (hyper branchedarchitecture) as structural matrix than mud acid modification, and make it import sulfonated polyaryl ether ketone polymer, constitute Semi-IPN formula cross-linked structure (semi-interpenetration network, semi-IPN), strengthen the water holding capacity of described ion/PEM thus, anti-chemistry, electrochemical stability and hear resistance, can be used for making membrane electrode group (membrane electrode assembly), fuel cell, or be applied to desalinization, the processing of heavy water and sewage, and give birth to field such as mass-energy source.
Description of drawings
Fig. 1 a to 1e shows the water conservation degree of the modified maleimide low polymer with different proportion branched structure;
Fig. 2 shows the heating-up temperature gradient of the heat cross-linking reaction of the embodiment of the invention 9 to 11;
Fig. 3 shows the heating-up temperature gradient of the heat cross-linking reaction of the embodiment of the invention 12 to 17; And
Fig. 4 shows the hot analysis result of TGA of S-PEEK and the high branched structure BMI of S-PEEK/ oligomer film.
The specific embodiment
The present invention is the exchange membrane that contains modified maleimide low polymer, comprise sulfonated polyaryl ether ketone polymer (Sulfonated poly (arylether ketone), S-PAEKS) and modified maleimide low polymer.Generally speaking, the weight ratio of described sulfonated polyaryl ether ketone polymer and described modified maleimide low polymer is in 99.95: 0.05 to 50: 50 scope, preferably, the weight ratio of described sulfonated polyaryl ether ketone polymer and described modified maleimide low polymer is in 99: 1 to 90: 10 scope.
Because PAEK base polymer (poly (arylether ketone), PAEKS) intermolecular hydrogen bonding effect meeting strengthens with the increase of sulfonated degree, by sulfonated further high-temperature stability, electrochemical stability and the electrical conductivity of improving the polyaryl ether ketone polymer.In an instantiation, utilize the concentrated sulfuric acid to carry out the sulfonating reaction of polyether-ether-ketone (PEEK):
By adjusting reaction condition and reaction environment, can obtain the sulfonated polyetheretherketonepolymer polymer (S-PEEKS) of different sulfonation degrees.Usually, the electrical conductivity of the polyaryl ether ketone polymer (S-PAEKS) of sulfonation degree 60% can reach 6 * 10
-2S/cm (25 ℃), the glass transition temperature of the polyaryl ether ketone polymer (S-PAEKS) of sulfonation degree 80% can be promoted to 210 ℃.Polyaryl ether ketone polymer through sulfonation has solvent compatibility preferably, helps to be mixed with the solution kenel, improves the manufacture method operation of film forming.Generally speaking, the sulfonation degree of sulfonated polyaryl ether ketone polymer of the present invention (S-PAEKS) is 5 to 95%, is preferably 45 to 75%.The example of described sulfonated polyaryl ether ketone polymer includes, but are not limited to sulfonated polyether-ketone polymer (S-PEK), sulfonated polyetheretherketonepolymer polymer (S-PEEK), sulfonated polyether-ether-ketone ketone polymer (S-PEEKK), reaches sulfonated polyetherketoneetherketoneketone polymer (S-PEKEKK).
In the exchange membrane of the present invention, has high branched structure (Hyper branched architecture) as the modified maleimide low polymer of structural matrix.Described modified maleimide be by barbituric acid or derivatives thereof or other can provide the reaction free radical initiator, carry out branching and preface reaction with maleimide.After certain reaction time, can carry out cessation reaction by the monomer that adds the maleimide or derivatives thereof, adjust the degree of branching and the degree of polymerization, control structure is organized configuration and molecular weight, acquisition has the modified maleimide low polymer of high branched structure, utilizes separation and leaching technology to separate out the similar oligomer of structural behaviour again.Described high branched structure can promote the dissolution with solvents degree of maleimide low polymer, increase compatibility with resin, can form composite with epoxy resin, polyimide resin or other resins easily, improve whole glass transition temperature, flintiness, heat endurance.
In an instantiation, the barbituric acid shown in the use formula (I) (Barbituric acid, BTA) or derivatives thereof:
(in the formula, R
1With R
2Be independently selected from-H ,-CH
3,-C
2H
5,-C
6H
5,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-CH
2CH
2CH (CH
3)
2Or-CH (CH
3)-CH
2-CH
2-CH
3)
With maleimide under the condition that solvent or cosolvent exist, link polymerisation and make.Described maleimide can be the BMI (BMI) shown in the formula (II):
(II) in the formula, R can be-(CH
2)
n-, 1≤n≤20;-[C (CH
2)
2]
M-, 1≤m≤20; ,-[CH
2-C (CH
3)
2]
p-, 1≤p≤10;
1≤p≤10);
Or be the BMI (BMI) shown in the formula (III):
(in the formula, Y can be R, SO
2, S, O, CONH, and C (CF
3)
2X
1～X
8Be independently selected from R, H, F, Cl, Br, HSO
3, SO
2).
The example of described BMI comprises, but be not limited to N, N '-ethene-BMI, N, N '-butylene-BMI, N, N '-hexa-methylene-BMI, N, N '-penylene-BMI, N, N '-4,4 '-diphenyl methane-BMI, N, N '-4,4 '-diphenyl ether-BMI, N, N '-4,4 '-diphenyl sulphone (DPS)-BMI, N, N '-4,4 '-dicyclohexyl methyl hydride-BMI, N, N '-4,4 '-xyxylene-BMI, and N, N ' 4, and 4 '--diphenyl cyclohexane-BMI.
In described instantiation, described BMI and described barbituric acid or derivatives thereof are 30: 1 to 3: 1 scope with mol ratio, are preferably 20: 1 to 10: 1 the anti-polymerisation that links of scope.The employed examples of solvents of described reaction includes, but are not limited to gamma-butyrolacton (γ-Butyrolactone), acrylic carbonic ester (PC), and N-methyl pyrrolidone (NMP).Preferably, with the solution of solid content 10 to 60 weight %,, stir and reacted in 0.5 to 6 hour 100 to 145 ℃ temperature range.
Modified maleimide low polymer with high branched structure used herein can be mixing in the solvent of for example N-methyl pyrrolidone with sulfonated polyaryl ether ketone polymer (S-PAEKS) easily, thermochemical crosslinking is carried out in heating, forms the exchange membrane with Semi-IPN formula cross-linked structure (semi-IPN).Modified maleimide low polymer as structural matrix in the exchange membrane of the present invention has high branched structure, and it has water holding capacity preferably.Fig. 1 a to 1e shows the water conservation degree of the modified maleimide low polymer with different proportion branched structure.Therefore, the present invention includes sulfonated polyaryl ether ketone polymer (S-PAEKS), and the exchange membrane of modified maleimide low polymer has preferable mechanical strength, and can increase glass transition temperature and heat endurance, promote water holding capacity simultaneously and reduce the swelling degree, and can avoid acidic materials to leach (acid leaching out) and increase the proton conversion ratio, and can have excellent anti-chemistry and electrochemical stability, can be used as ion/PEM, be used to make membrane electrode group (membrane electrode assembly), fuel cell, or be applied to desalinization, the processing of heavy water and sewage, and give birth to field such as mass-energy source.
Below further specify characteristics of the present invention and effect by particular specific embodiment, but be not to be used to limit category of the present invention.
Embodiment
Synthesis example 1: the preparation of modified bismaleimide oligomer
With reactant N, N '-4,4 '-diphenyl methane-BMI, and barbituric acid (mol ratio 10: 1) places reaction vessel, gamma-butyrolacton added in the reaction vessel again, solid content is 20 weight %.Be heated to 130 ℃ after the mixing and react, last 5 hours, obtain modified maleimide low polymer.
Synthesis example 2: the preparation of sulfonated polyether-ether-ketone (sulfonated degree 93%)
(Vitrex PF 450) placed baking oven with the polyether-ether-ketone powder, in 110 ℃ of bakings 2 hours.Polyether-ether-ketone powder after the oven dry is placed single neck round-bottomed flask, slowly add the concentrated sulfuric acid (95～98%), the weight ratio of the polyether-ether-ketone powder and the concentrated sulfuric acid is 1: 10.Utilize mechanical agitation, rotating speed 900rpm is warming up to 45 ℃, feeds nitrogen and reacts, and reaction lasts 7 hours.After the question response time arrives, pour into solution in the frozen water and stirring simultaneously, make formed sulfonated polyether-ether-ketone (S-PEEK) precipitation.Then, utilize washed with de-ionized water to the pH value of solution value greater than 6.The sulfonated polyetheretherketonepolymer polymer of gained is placed 80 ℃ of baking ovens, after removing most of moisture content, be warming up to 110 ℃ and vacuumized 2 hours again, obtain the sulfonated polyetheretherketonepolymer polymer (sulfonated degree is about 93%) of yellow solid, and it is stored in the drying box.
Synthesis example 3: the preparation of sulfonated polyether-ether-ketone (sulfonated degree 56%)
(Vitrex PF 450) placed baking oven with the polyether-ether-ketone powder, in 110 ℃ of bakings 2 hours.Polyether-ether-ketone powder after the oven dry is placed single neck round-bottomed flask, slowly add the concentrated sulfuric acid (95～98%) ice bath simultaneously, the weight ratio of the polyether-ether-ketone powder and the concentrated sulfuric acid is 1: 10.Utilized mechanical agitation 1 hour under ice bath, rotating speed 900rpm dissolves polyetheretherketonepolymer polymer fully, is warming up to 45 ℃ after the dissolving and continues to react and last 7 hours.After the question response time arrives, pour into solution in the frozen water and stirring simultaneously, make formed sulfonated polyether-ether-ketone (S-PEEK) precipitation.Then, utilize washed with de-ionized water to the pH value of solution value greater than 6.The sulfonated polyetheretherketonepolymer polymer of gained is placed 80 ℃ of baking ovens, after removing most of moisture content, be warming up to 110 ℃ and vacuumized 2 hours again, obtain the sulfonated polyetheretherketonepolymer polymer (sulfonated degree is about 56%) of yellow solid, and it is stored in the drying box.
Comparative example 1: the preparation of sulfonated polyether-ether-ketone film
Sulfonated polyether-ether-ketone (S-PEEK) polymer is placed serum bottle, add N-methyl pyrrolidone (NMP) solvent.Serum bottle is placed 80 ℃ of oil bath pans, and stirring makes S-PEEK be dissolved in nmp solvent, but forms coating solution, and its solid content is 10 weight %.Utilize the scraper of 1500 microns of slit gaps, sulfonated polyether-ether-ketone solution coat on glass substrate, and is placed in 80 ℃ of baking ovens and toasts film forming.Be warming up to 110 ℃ and vacuumized 2 hours after the film forming again, remove residual solvent.At last, prepared sulfonated polyether-ether-ketone film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain the sulfonated polyether-ether-ketone film of golden transparent, thickness is about 80～120 microns.
Test case
(water uptake, WU) (solvent uptake, measurement SU) is that film sample is dipped in the methanol solution of distilled water, 10vol%, the methanol solution of 30vol% respectively to water absorption rate, is heated to 60 ℃ and lasts 1 hour with the solvent absorptivity.Sample was placed 80 ℃ of vacuum drying ovens dry 2 hours, then weighing.Calculate water absorption rate and solvent absorptivity according to following formula
WU/SU=(W
Wet-W
Do)
/W
Do* 100%
W
WetWith W
DoRepresent dry film weight and swelling film respectively
Embodiment 1
The modified maleimide low polymer that synthesis example 1 is obtained is added in the sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) that synthesis example 2 obtained, the modified maleimide low polymer adding proportion is 1 weight %, add nmp solvent again, the weight ratio of described sulfonated polyetheretherketonepolymer polymer and nmp solvent is 1: 10.Mixture is placed ultrasonic oscillation instrument concussion dissolving, at room temperature solution is evenly mixed again after the dissolving, obtain the thick solution of glassy yelloe.Utilize the scraper of 1500 microns of slit gaps, solution coat in glass substrate, is carried out the heat cross-linking reaction in 180 ℃ baking oven, last 6 hours.At last, prepared film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain isabelline transparent sulfonated polyether-ether-ketone/have the modified bismaleimide oligomer film of high branched structure, thickness is about 80～120 microns.Film forming and property detection result are embedded in table 1 and table 2 respectively.
Embodiment 2-4
Repeat the step of embodiment 1, the addition with modified maleimide low polymer changes 2 weight %, 3.5 weight % into, reaches 5 weight % respectively.Film forming and property detection result are embedded in table 1 and table 2 respectively.
Embodiment 5
The modified maleimide low polymer that synthesis example 1 is obtained is added into the sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) that synthesis example 2 is obtained, adding proportion is 1 weight %, add nmp solvent again, the weight ratio of described sulfonated polyetheretherketonepolymer polymer and nmp solvent is 1: 10.Mixture is placed ultrasonic oscillation instrument concussion dissolving, at room temperature solution is evenly mixed again after the dissolving, obtain the thick solution of glassy yelloe.Utilize the scraper of 1500 microns of slit gaps, solution coat in glass substrate, is carried out the heat cross-linking reaction in 180 ℃ baking oven, last 20 hours.At last, prepared film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain isabelline transparent sulfonated polyether-ether-ketone/have the modified bismaleimide oligomer film of high branched structure, thickness is about 80～120 microns.Film forming and property detection result are embedded in table 1 and table 2 respectively.
Embodiment 6-8
Repeat the step of embodiment 5, the addition with modified maleimide low polymer changes 2 weight %, 3.5 weight % into, reaches 5 weight % respectively.Film forming and property detection result are embedded in table 1 and table 2 respectively.
Table 1
| Reaction temperature/time | Sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) | Modified maleimide low polymer (synthesis example 1) | Outward appearance | |
| Comparative example 1 | 80℃ | 100 | - | The golden transparent forming thin film is good, the tool pliability |
| Embodiment 1 | 180 ℃/6 hours | 99 | 1 | Brown transparent membrane film forming is good, the |
| Embodiment | ||||
| 2 | 98 | 2 | The transparent membrane film forming is good, the tool pliability |
| Embodiment 3 | 96.5 | 3.5 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 4 | 95 | 5 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 5 | 180 ℃/20 hours | 99 | 1 | The transparent membrane film forming is good, the |
| Embodiment | ||||
| 6 | 98 | 2 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 7 | 96.5 | 3.5 | The transparent membrane film forming is good, the | |
| Embodiment | ||||
| 8 | 95 | 5 | The transparent membrane film forming is good, the tool pliability |
Table 2
| WU(％) | SU (10vol％) | SU (30vol％) | σ(S/cm) | Thickness (micron) | Resistance (Ω) | |
| Comparative example 1 | 137 | - | - | 2.63×10 -2 | 440 | 2.5 |
| Embodiment 1 | 52.8 | 45.1 | 752.6 | 1.36×10 -2 | 100 | 1.1 |
| |
51.4 | 22.5 | 307.8 | 9.07×10 -3 | 80 | 1.3 |
| Embodiment 3 | 51.7 | 62.3 | 104.4 | 7.52×10 -3 | 130 | 2.6 |
| Embodiment 4 | 47.3 | 58.2 | 102.3 | 6.67×10 -3 | 100 | 2.2 |
| Embodiment 5 | 44.95 | 50.6 | 61.61 | 5.84×10 -3 | 180 | 4.6 |
| |
36.36 | 46.4 | 58.33 | 3.72×10 -3 | 160 | 6.4 |
| Embodiment 7 | 30.22 | 37.58 | 50.43 | 2.29×10 -3 | 200 | 13.0 |
| Embodiment 8 | 38.32 | 64.81 | 68.69 | 1.04×10 -3 | 80 | 11.5 |
The above results shows that the electrical conductivity of film descends along with the increase of high branched structure bismaleimide amine oligomer content of crosslinking agent, and the time of film heat cross-linking, the degree that influences electrical conductivity was also just big when longer.Promptly, under the same conditions, increase crosslinking time, high branched structure bismaleimide amine oligomer formed cross-linked structure in the S-PEEK macromolecule is also just more complete, therefore has the effect that clearly reduces the film swelling for film in water or methanol solution.
Fig. 4 is the hot analysis result of TGA of S-PEEK and the high branched structure BMI of S-PEEK/ oligomer film.In thermogravimetric loss temperature is the loss of hydrone for about 170 ℃, and the S-PEEK film of comparative example 1 all hydrones that before temperature is 100 ℃, run off, promptly simple S-PEEK film does not have water-retaining property under the environment more than 100 ℃.But when high branched structure bismaleimide amine oligomer forms fine and close cross-linked structure in the S-PEEK macromolecule, then moisture content there is good reservation effect.About 340 ℃ of thermogravimetric loss temperature, cracking for sulfonate radical, and embodiment 4,5, and 8 all be higher than the S-PEEK film in this temperature, show that high branched structure bismaleimide amine oligomer crosslinking agent forms cross-linked structure really and stablized the heat endurance of sulfonate radical in macromolecule.
Embodiment 9
The modified maleimide low polymer that synthesis example 1 is obtained is added into the sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) that synthesis example 2 is obtained, adding proportion is 1 weight %, add nmp solvent again, the weight ratio of described sulfonated polyetheretherketonepolymer polymer and nmp solvent is 1: 10.Mixture is placed ultrasonic oscillation instrument concussion dissolving, at room temperature solution is evenly mixed again after the dissolving, obtain the thick solution of glassy yelloe.Utilize the scraper of 1500 microns of slit gaps, solution coat on glass substrate, is carried out the heat cross-linking reaction according to the thermograde that Fig. 2 illustrated.At last, prepared film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain isabelline transparent sulfonated polyether-ether-ketone/have the modified bismaleimide oligomer film of high branched structure, thickness is about 80～120 microns.Film forming and property detection result are embedded in table 3 and table 4 respectively.
Repeat the step of embodiment 9, the addition with modified maleimide low polymer changes 2 weight % into, reaches 5 weight % respectively.Film forming and property detection result are embedded in table 3 and table 4 respectively.
The modified maleimide low polymer that synthesis example 1 is obtained is added into the sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) that synthesis example 2 is obtained, adding proportion is 2 weight %, add nmp solvent again, the weight ratio of described sulfonated polyetheretherketonepolymer polymer and nmp solvent is 1: 10.Mixture is placed ultrasonic oscillation instrument concussion dissolving, at room temperature solution is evenly mixed again after the dissolving, obtain the thick solution of glassy yelloe.Utilize the scraper of 1500 microns of slit gaps, solution coat in glass substrate, is carried out the heat cross-linking reaction according to the thermograde that Fig. 3 illustrated.At last, prepared film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain isabelline transparent sulfonated polyether-ether-ketone/have the modified bismaleimide oligomer film of high branched structure, thickness is about 80～120 microns.Film forming and property detection result are embedded in table 3 and table 4 respectively.
Repeat the step of embodiment 12, the addition with modified maleimide low polymer changes 3.5 weight % into, reaches 5 weight % respectively.Film forming and property detection result are embedded in table 3 and table 4 respectively.
Table 3
| Reaction temperature/time | Sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) | Modified maleimide low polymer (synthesis example 1) | Outward appearance | |
| Comparative example 1 | 80℃ | 100 | - | The golden transparent forming thin film is good, the tool pliability |
| Embodiment 9 | (with reference to figure 2) | 99 | 1 | Brown transparent membrane film forming is good, the |
| Embodiment | ||||
| 10 | 98 | 2 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 11 | 95 | 5 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 12 | (with reference to figure 3) | 98 | 2 | The transparent membrane film forming is good, the tool pliability |
| Embodiment 13 | 96.5 | 3.5 | The transparent membrane film forming is good, the | |
| Embodiment | ||||
| 14 | 95 | 5 | The transparent membrane film forming is good, the tool pliability |
Table 4
| WU(％) | SU(30vol％) | σ(S/cm) | |
| Embodiment 9 | 1756 | - | 1.10×10 -2 |
| |
332 | 928 | 2.82×10 -2 |
| Embodiment 11 | 184 | 606 | 1.43×10 -2 |
| |
123 | NA | 8.28×10 -3 |
| Embodiment 13 | 691 | NA | 1.00×10 -2 |
| |
1333 | NA | 8.32×10 -3 |
The above results shows that film is after adding high branched structure bismaleimide amine oligomer crosslinking agent, and electrical conductivity does not decline to a great extent, even when the crosslinking agent of 5 weight %, its electrical conductivity still has 1.43 * 10
-2S/cm.In the measurement result of water absorption rate (Water uptake), the film of embodiment 9 is because only add the high branched structure bismaleimide of 1 weight % amine oligomer crosslinking agent, so can't suppress the swelling of film higher water absorption is arranged, but simple S-PEEK film is dissolving fully already under 60 ℃, by contrast, the adding of high branched structure bismaleimide amine oligomer crosslinking agent promotes the hear resistance and the anti swelling of S-PEEK film, shows the advantage of its gain film characteristics function.Along with the increase of high branched structure bismaleimide amine oligomer crosslinking agent, the water absorption that suppresses film is also just more obvious.Though the film of embodiment 9 still has the ability that suppresses swelling slightly in water, yet in the 30vol% methanol aqueous solution, but can't resist the destruction of methyl alcohol and produce the phenomenon of dissolving, but the situation of this dissolving reduces along with the increase of high branched structure bismaleimide amine oligomer content of crosslinking agent.
Among the shown result of embodiment 12-14, electrical conductivity can't make electrical conductivity descend along with the increase of high branched structure bismaleimide amine oligomer crosslinking agent.Therefore add temperature program,, show good effect for the even dispersion of crosslinking agent and keeping of electrical conductivity.
Embodiment 15
The modified maleimide low polymer that synthesis example 1 is obtained is added in the sulfonated polyetheretherketonepolymer polymer (sulfonated degree 56%) that synthesis example 3 obtained, adding proportion is 2 weight %, add nmp solvent again, the weight ratio of described sulfonated polyetheretherketonepolymer polymer and nmp solvent is 1: 10.Mixture is placed ultrasonic oscillation instrument concussion dissolving, at room temperature solution is evenly mixed again after the dissolving, obtain the thick solution of glassy yelloe.Utilize the scraper of 1500 microns of slit gaps, solution coat on glass substrate, is carried out the heat cross-linking reaction according to the thermograde that Fig. 3 illustrated.At last, prepared film is soaked in 60 ℃ the 0.5M sulfuric acid solution, carries out 2 hours acid cleaning process.Place 60 ℃ deionized water to wash after the pickling again, be washed to pH value of water solution greater than more than 6.Obtain isabelline transparent sulfonated polyether-ether-ketone/have the modified bismaleimide oligomer film of high branched structure, thickness is about 80～120 microns.Film forming and property detection result are embedded in table 5 and table 6 respectively.
Repeat the step of embodiment 15, the addition with modified maleimide low polymer changes 3.5 weight % into, reaches 5 weight % respectively.Film forming and property detection result are embedded in table 5 and table 6 respectively.
Table 5
| Reaction temperature/time | Sulfonated polyetheretherketonepolymer polymer (sulfonated degree 93%) | Modified maleimide low polymer (synthesis example 1) | Outward appearance | |
| Comparative example 1 | 80℃ | 100 | - | The golden transparent forming thin film is good, the tool pliability |
| Embodiment 15 | (with reference to figure 3) | 98 | 2 | Brown transparent membrane film forming is good, the |
| Embodiment | ||||
| 16 | 96.5 | 3.5 | The transparent membrane film forming is good, the tool pliability | |
| Embodiment 17 | 95 | 5 | The transparent membrane film forming is good, the tool pliability |
Table 6
| WU(％) | σ(S/cm) | |
| Embodiment 15 | 19 | 4.09×10 -3 |
| |
23 | 7.74×10 -3 |
| Embodiment 17 | 39 | 2.69×10 -3 |
The above results shows, uses the prepared film that comes out of the S-PEEK of 56% sulfonated degree, and its prepared film that comes out has good film forming and flexibility.Be to use the S-PEEK of kullgren acid degree in this program, the electrical conductivity of the therefore prepared film that comes out all can be lower than previous embodiment.The thermograde program of this film is identical with embodiment 12～14, and its electrical conductivity increases along with high branched structure bismaleimide amine oligomer crosslinking agent and descends.Aspect water absorption, the water absorption of film obviously increases along with the increase of content of crosslinking agent.
Comprehensive The above results shows that high branched structure bismaleimide amine oligomer crosslinking agent can form crosslinked network structure really in the S-PEEK macromolecule, and effectively suppresses excessive swelling or the dissolution phenomena of film in water or methanol solution.But still need decide on the sulfonated degree of structure, content, crosslinking time and the S-PEEK of crosslinking agent for the electrical conductivity of film and the balance between the swelling.In addition, the thermograde program technic, it not only can make crosslinking agent more even in film, also can allow the micro-structural of S-PEEK form more complete, and can control cross-linked speed during crosslinked by the program of this temperature control, make crosslinking agent in macromolecule, form more complete and fine and close network structure.
The foregoing description and comparative example are only done illustrative principle of the present invention and effect thereof, but not are used to limit the present invention.Any those skilled in the art all can be under spirit of the present invention and category, and above-mentioned example is modified and changed.Therefore, the scope of the present invention, claims are listed as described later.
Claims (20)
1. exchange membrane that contains modified maleimide low polymer comprises sulfonated polyaryl ether ketone polymer (S-PAEKS) and as the modified maleimide low polymer of structural matrix.
2. exchange membrane according to claim 1, wherein, the weight ratio of described sulfonated polyaryl ether ketone polymer and described modified maleimide low polymer is in 99.95: 0.05 to 50: 50 the scope.
3. exchange membrane according to claim 1, wherein, the weight ratio of described sulfonated polyaryl ether ketone polymer and described modified maleimide low polymer is in 99: 1 to 90: 10 the scope.
4. exchange membrane according to claim 1, wherein, the sulfonation degree of described sulfonated polyaryl ether ketone polymer is 5 to 95%.
5. exchange membrane according to claim 1, wherein, the sulfonation degree of described sulfonated polyaryl ether ketone polymer is 45 to 75%.
6. exchange membrane according to claim 1, wherein, described sulfonated polyaryl ether ketone polymer is selected from sulfonated polyether-ketone polymer (S-PEK), sulfonated polyetheretherketonepolymer polymer (S-PEEK), sulfonated polyether-ether-ketone ketone polymer (S-PEEKK) or sulfonated polyetherketoneetherketoneketone polymer (S-PEKEKK).
7. exchange membrane according to claim 1, wherein, described modified maleimide low polymer has high branched structure (hyper branched architecture).
8. exchange membrane according to claim 1, wherein, described modified maleimide low polymer is that to carry out the heat cross-linking reaction of free radical partly by barbituric acid or derivatives thereof and BMI formed.
9. exchange membrane according to claim 8, wherein, described barbituric acid has the structure shown in the following formula (I):
In the formula, R
1With R
2Be independently selected from-H ,-CH
3,-C
2H
5,-C
6H
5,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-CH
2CH
2CH (CH
3)
2, or-CH (CH
3)-CH
2-CH
2-CH
3
10. exchange membrane according to claim 8, wherein, described BMI has the structure shown in the following formula (II):
In the formula, R is independently selected from-(CH
2)
n-, 1≤n≤20;-[C (CH
2)
2]
M-, 1≤m≤20; ,-[CH
2-C (CH
3)
2]
p-, 1≤p≤10;
1≤p≤10);
11. exchange membrane according to claim 8, wherein, described BMI has the structure shown in the following formula (III):
In the formula, Y is selected from R, SO
2, S, O, CONH, or C (CF
3)
2X
1～X
8Be independently selected from R, H, F, Cl, Br, HSO
3, SO
2
12. exchange membrane according to claim 8, wherein, described BMI is selected from N, N '-ethene-BMI, N, N '-butylene-BMI, N, N '-hexa-methylene-BMI, N, N '-penylene-BMI, N, N '-4,4 '-diphenyl methane-BMI, N, N '-4,4 '-diphenyl ether-BMI, N, N '-4,4 '-diphenyl sulphone (DPS)-BMI, N, N '-4,4 '-dicyclohexyl methyl hydride-BMI, N, N '-4,4 '-xyxylene-BMI or N, N '-4,4 '-diphenyl cyclohexane-BMI.
13. exchange membrane according to claim 8, wherein, the mol ratio of described BMI and described barbituric acid is 30: 1 to 3: 1 a scope.
14. exchange membrane according to claim 8, wherein, the mol ratio of described BMI and described barbituric acid is 20: 1 to 10: 1 a scope.
15. exchange membrane according to claim 8, wherein, described reaction is to carry out under the condition that solvent exists.
16. exchange membrane according to claim 15, wherein, described solvent is selected from gamma-butyrolacton, acrylic carbonic ester or N-methyl pyrrolidone.
17. exchange membrane according to claim 1, its have Semi-IPN formula cross-linked structure (semi-interpenetration, semi-IPN).
18. exchange membrane according to claim 1 is used as amberplex.
19. exchange membrane according to claim 1 is used as PEM.
20. exchange membrane according to claim 1 can be used for making membrane electrode group and fuel cell, or is applied to the processing of desalinization, heavy water and sewage, and gives birth to field such as mass-energy source.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8008360B2 (en) | 2008-11-27 | 2011-08-30 | Industrial Technology Research Institute | Proton exchange membrane and method for manufacturing the same |
| CN101931086B (en) * | 2009-06-25 | 2012-12-12 | 财团法人工业技术研究院 | Interpenetrated reticular proton exchange membrane, forming method thereof and proton exchange membrane fuel cell |
| CN101997125B (en) * | 2009-08-14 | 2013-07-10 | 财团法人工业技术研究院 | Modified hyperbranched polymer (HBP), proton exchange membrane prepared by using same and preparation method of proton exchange membrane |
| US9267005B2 (en) | 2011-12-29 | 2016-02-23 | Industrial Technology Research Institute | Flexible maleimide polymer and method for preparing the same |
| CN108070084A (en) * | 2016-11-18 | 2018-05-25 | 王復民 | oligomer polymer and lithium battery |
| CN114181528A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Thermoplastic polyimide composition and application thereof, and preparation and application of thermoplastic polyimide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2959060B2 (en) * | 1990-07-04 | 1999-10-06 | 東ソー株式会社 | Separation membrane |
| US5534146A (en) * | 1994-06-15 | 1996-07-09 | Netwig; Craig L. | Process for producing in SITU polymerization of a reverse osmosis membrane and product therefrom |
| CN1220753C (en) * | 2002-12-19 | 2005-09-28 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing polyimide liquid crystal oriented membrane at constant temperature |
| DE10309135A1 (en) * | 2003-02-28 | 2004-09-09 | Basf Ag | Process for the preparation of a polymer system capable of proton exchange based on polyaryl ether ketones |
-
2007
- 2007-10-16 CN CN2007101624962A patent/CN101219349B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8008360B2 (en) | 2008-11-27 | 2011-08-30 | Industrial Technology Research Institute | Proton exchange membrane and method for manufacturing the same |
| CN101931086B (en) * | 2009-06-25 | 2012-12-12 | 财团法人工业技术研究院 | Interpenetrated reticular proton exchange membrane, forming method thereof and proton exchange membrane fuel cell |
| CN101997125B (en) * | 2009-08-14 | 2013-07-10 | 财团法人工业技术研究院 | Modified hyperbranched polymer (HBP), proton exchange membrane prepared by using same and preparation method of proton exchange membrane |
| US9267005B2 (en) | 2011-12-29 | 2016-02-23 | Industrial Technology Research Institute | Flexible maleimide polymer and method for preparing the same |
| CN108070084A (en) * | 2016-11-18 | 2018-05-25 | 王復民 | oligomer polymer and lithium battery |
| CN114181528A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Thermoplastic polyimide composition and application thereof, and preparation and application of thermoplastic polyimide |
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| CN101219349B (en) | 2011-07-20 |
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Inventor after: Pan Jinping Inventor after: Wang Zongxiong Inventor after: Xu Rongmu Inventor after: Zhu Bairen Inventor after: Wu Qianshun Inventor after: Liu Baijun Inventor before: Pan Jinping Inventor before: Wang Zongxiong Inventor before: Xu Rongmu Inventor before: Zhu Bairen Inventor before: Wu Qianshun Inventor before: Liu Baijun |